US11390632B2ActiveUtilityA1

Process for the preparation of 7-(4,7-diazaspiro[2.5]octan-7-yl)-2-(2,8-dimethylimidazo [1,2-B]pyridazin-6-yl)pyrido[1,2-a]pyrimidin-4-one derivatives

90
Assignee: HOFFMANN LA ROCHEPriority: Sep 22, 2017Filed: Mar 19, 2020Granted: Jul 19, 2022
Est. expirySep 22, 2037(~11.2 yrs left)· nominal 20-yr term from priority
C07D 487/04C07D 471/04C07D 401/04B01J 23/755B01J 23/44A61K 31/519A61K 31/496C07D 519/00
90
PatentIndex Score
3
Cited by
10
References
26
Claims

Abstract

The present invention relates to a process for the preparation of 7-(4,7-diazaspiro[2.5]octan-7-yl)-2-(2,8-dimethylimidazo[1,2-b]pyridazin-6-yl)pyrido[1,2-a]pyrimidin-4-one derivatives useful as pharmaceutically active compounds.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A process for the preparation of a compound of formula (II) 
       
         
           
           
               
               
           
         
         which comprises reacting a compound of formula (III) 
       
       
         
           
           
               
               
           
         
         with a compound of formula (III′), (III a ′) or (III b ′) 
       
       
         
           
           
               
               
           
         
         in the presence of a palladium catalyst or nickel catalyst to form the compound of formula (II), wherein X is selected from an alkyl, aryl sulfonate, fluorinated alkyl, fluorinated aryl sulfonate and halide. 
       
     
     
       2. The process of  claim 1 , wherein the compound of formula (III) is reacted with the compound of formula (III′), (III a ′) or (III b ′) in presence of a palladium catalyst. 
     
     
       3. The process of  claim 1 , wherein X is selected from the group consisting of pTolSO 3— , CH 3 SO 3— , phenyl-SO 3— , CF 3 SO 3— , nonaflate, Cl, Br, and I. 
     
     
       4. The process of  claim 1 , wherein said process is carried out in the presence of a base. 
     
     
       5. The process of  claim 4 , wherein the base is selected from the group consisting of Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 , KOAc and KOtBu. 
     
     
       6. The process of  claim 5 , wherein the base is K 2 CO 3 . 
     
     
       7. The process of  claim 4 , wherein said process is carried out in the presence of a palladium catalyst and base. 
     
     
       8. The process of  claim 1 , wherein the compound of formula (III) is reacted with the compound of formula (III′). 
     
     
       9. The process of  claim 8 , wherein said process further comprises
 reacting a compound having formula 
 
       
         
           
           
               
               
           
         
         with bis(pinacolato)diboron to obtain the compound of formula (III′): 
       
       
         
           
           
               
               
           
         
       
     
     
       10. The process of  claim 1 , wherein said process further comprises
 reacting a compound of formula (IV) 
 
       
         
           
           
               
               
           
         
       
       with
 tosyl chloride when X is pTol—SO 3— , 
 methanesulfonyl chloride when X is CH 3 SO 3— , 
 triflyl chloride when X is CF 3 SO 3— or 
 phenylsulfonylchloride when X is phenyl—SO 3— , 
 
       in the presence of a base; or with
 POCl 3  when X is Cl, 
 POBr 3  when X is Br, or 
 Ph 3 PI 2  or POCl 3  followed by NaI or CuI, when X is I 
 
       for the preparation of the compound of formula (III) 
       
         
           
           
               
               
           
         
       
     
     
       11. The process of  claim 10 , wherein the base is an organic base or basic alkali metal salts. 
     
     
       12. The process of  claim 11 , wherein the base is nitrogen-containing heterocycle, tertiary amine or basic alkali metal salts. 
     
     
       13. The process of  claim 12 , wherein the base is a tertiary amine. 
     
     
       14. The process of  claim 10 , wherein said process further comprises
 reacting a compound of formula (V) 
 
       
         
           
           
               
               
           
         
         with di-tert-butyl malonate for the preparation of the compound of formula (IV) 
       
       
         
           
           
               
               
           
         
       
     
     
       15. The process of  claim 14 , wherein said process is carried out in the presence of xylene, dichlorobenzene, toluene or anisole. 
     
     
       16. The process according to  claim 15 , wherein said process is carried out in the presence of anisole. 
     
     
       17. The process of  claim 14 , said process further comprising reducing a compound of formula (VI) 
       
         
           
           
               
               
           
         
         to provide the compound of formula (V) 
       
       
         
           
           
               
               
           
         
       
     
     
       18. The process of  claim 17 , wherein reducing a compound of formula (VI) comprises reacting said compound with a transition metal hydrogenation catalyst to obtain the compound of formula (V). 
     
     
       19. The process according to  claim 18 , wherein the transition metal hydrogenation catalyst is selected from the group consisting of a Raney catalyst, Pd/C, Pd(OH) 2 /C, Au/TiO 2 , Rh/C, Ru/Al 2 O 3 , Ir/CaCO 3 , Pt-V/C, Pt/C and combinations thereof. 
     
     
       20. The process according to  claim 19 , wherein the transition metal hydrogenation catalyst is Pt-V/C. 
     
     
       21. The process according to  claim 20 , wherein the transition metal hydrogenation catalyst is Pt 1% and V 2% on activated carbon. 
     
     
       22. The process of  claim 17 , said process further comprising
 reacting a compound of formula (VII) 
 
       
         
           
           
               
               
           
         
         with a compound of formula (VIII) 
       
       
         
           
           
               
               
           
         
         or a salt thereof for the preparation of the compound of formula (VI) 
       
       
         
           
           
               
               
           
         
       
     
     
       23. The process of  claim 22 , wherein the salt is an oxalate salt. 
     
     
       24. A process for the preparation of a compound of formula (I) 
       
         
           
           
               
               
           
         
         said process comprising 
         preparing a compound of formula (II) comprising 
       
       
         
           
           
               
               
           
         
         reacting a compound of formula (III) 
       
       
         
           
           
               
               
           
         
         with a compound of formula (III′), (III a ′) or (III b ′) 
       
       
         
           
           
               
               
           
         
         in the presence of a palladium catalyst or nickel catalyst to form the compound of formula (II), wherein X is selected from an alkyl, aryl sulfonate, fluorinated alkyl, fluorinated aryl sulfonate and halide; and 
         reacting the compound of formula (II) 
       
       
         
           
           
               
               
           
         
         with a strong acid for the preparation of a compound of formula (I) or a pharmaceutically acceptable salt thereof. 
       
     
     
       25. The process of  claim 24 , wherein the strong acid is HCl. 
     
     
       26. The process of  claim 25 , wherein the HCl is made in situ with 1-propanol and acetyl chloride.

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